Process for the preparation of azidoperfluoroalkanes and N-polyfluoroalkyl azides

ABSTRACT

Process for the preparation of azidoperfluoroalkanes and azidopolyfluoroalkanes of general formula R F —N 3 , where R F  is chosen from a group containing C n F 2n+1 , C n F x H 2n+1−x , C n F x X 2n+1−x  or R 1 CF 2 CF 2 , where n is an integer in the range of 1 to 10, x is an integer in the range of 2 to 20, X is Cl, Br, or I, R 1  is C 1-10  alkyl, ArO, ArS, imidazolyl, benzimidazolyl, or pyrazolyl and Ar is phenyl or substituted phenyl, by the reaction of electrophilic azidation reagent of general formula R 2 —N 3 , where R 2  is n-C 4 F 9 SO 2 , ArSO 2 , Br, I, with synthetic equivalent of polyfluoroalkylated carbanion of general formula [R F ] − .

FIELD OF THE INVENTION

The invention relates to methods of preparation of azidopolyfluoroalkanes by the reaction of synthetic equivalents of polyfluoroalkyl carbanions with electrophilic azidation reagents and to the use of azidopolyfluoroalkanes in the preparation of N-polyfluoroalkyl triazoles.

BACKGROUND ART

Organic compounds containing the trifluoromethyl group, perfluoroalkyl or polyfluoroalkyl groups find use as crop protection agents, pharmaceuticals and functional materials. In drugs, for example, the trifluoromethyl group is introduced mainly to increase metabolic stability and lipophilicity, to modulate the pK_(a) of neighboring ionizable functional groups, and to impart weak C—F⋅⋅⋅X interaction. Compounds with perfluoroalkyl or polyfluoroalkyl groups connected to the nitrogen atom are rare and the methods of their preparation have hardly been explored. These compounds have a high potential to display unique physico-chemical and biological properties.

Organic azides are valuable intermediates in synthetic chemistry. Their ability to react with nucleophiles or electrophiles, to access nitrene chemistry by N₂ elimination, or to act as dipoles in cycloadditions, underscores their versatility. The so called click reaction—Cu(I)-catalyzed azide alkyne cycloaddition (CuAAC)—is a robust, effective and selective process widely used in organic synthesis, medicinal chemistry, in the chemistry of polymers and in chemical biology. Azidotrifluoromethane (CF₃N₃) is a known compound, which is thermally stable up to 300° C. and it was previously prepared in two steps from trifluoronitrosomethane (CF₃NO) [K. O. Christe, C. J. Schack, Inorg. Chem. 1981, 20, 2566-2570]. The need to use not easily accessible starting materials, toxic and corrosive reagents and difficult synthesis precludes the use and investigation of properties of CF₃N₃. Longer carbon chain azidoperfluoroalkanes are not known, some azidopolyfluoroalkanes have been synthesized through the reaction of sodium azide with polyfluoroalkenes [C. G. Krespan, B. E. Smart, J. Org. Chem. 1986, 51, 320-326] or with halodifluoromethyl compounds [T. G. Archibald, K. Baum, J. Org. Chem. 1990, 55, 3562-3565]. In order to accelerate the development of applications and commercialization of CF₃N₃, azidoperfluoroalkanes and azidopolyfluoroalkanes, a more straightforward synthetic method is needed.

DISCLOSURE OF THE INVENTION

Object of the invention is a process for the preparation of azidoperfluoroalkanes and azidopolyfluoroalkanes of formula R_(F)—N₃,

-   -   wherein R_(F) is selected from the group consisting of         C_(n)F_(2n+1), C_(n)F_(x)H_(2n+1−x), C_(n)F_(x)X_(2n+1−x) or         R¹CF₂CF₂, wherein n is an integer in the interval from 1 to 10,         x is an integer in the interval from 2 to 20 and     -   X is Cl, Br, or I,     -   R¹ is selected from the group consisting of C₁₋₁₀ alkyl, ArO,         ArS, imidazolyl, benzimidazolyl, or pyrazolyl, wherein Ar is         phenyl or substituted phenyl,         said process having the following steps

-   (A) generation of a synthetic equivalent of polyfluoroalkyl     carbanion, said synthetic equivalent having the formula [R_(F)]⁻, by     a method selected from:

-   a) activation of trialkyl(polyfluoroalkyl)silane of general formula     R³ ₃SiR_(F), wherein R³ is C₁₋₅ alkyl, with a Lewis base which is     selected from the group consisting of potassium fluoride, cesium     fluoride, tetramethylammonium fluoride, tetrabutylammonium fluoride,     sodium carbonate, potassium carbonate, potassium phosphate, sodium     acetate, potassium acetate, tetrabutylammonium acetate;

-   b) reaction of polyfluoroalkane of general formula RFH with a base     which is selected from a group consisting of methyllithium,     butyllithium, phenyllithium, Grignard reagent of general formula     R³MgX, wherein R³ is C₁₋₅ alkyl, and complexes of these compounds     with LiCl;

-   c) reaction of halopolyfluoroalkane of general formula R_(F)Br or     R_(F)I with metalation reagents, which are selected from a group     consisting of methyllithium, butyllithium, Grignard reagent of     general formula R³MgX, wherein R³ is C₁₋₅ alkyl, and complexes of     these compounds with LiCl,

-   under temperature in the range from −78° C., or from the melting     point of the reaction mixture, to +60° C.,

-   (B) reaction of an electrophilic azidation reagent of general     formula R²—N₃,     -   wherein R² is selected from the group consisting of n-C₄F₉SO₂,         ArSO₂, Br, and I,     -   wherein Ar is phenyl or substituted phenyl,         with the synthetic equivalent of polyfluoroalkyl carbanion of         general formula [R_(F)]⁻ generated in step (A).

“Substituted phenyl” represents a phenyl substituted by at least one substitutent, preferably selected from C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen, nitro, C₁-C₄ perfluoroalkyl.

In one aspect of the method, the reaction is preferably performed in the presence of at least equimolar amount of polyfluoroalkylated carbanion of general formula [R_(F)]⁻ or trialkyl(polyfluoroalkyl)silane activated with a Lewis base.

In another embodiment of the method, the polyfluoroalkylated carbanion synthetic equivalents are generated from:

-   -   CF₃SiMe₃ or n-C₃F₇SiMe₃ or n-C₈F₇SiMe₃ activated with cesium         fluoride, preferably in dimethylformamide at a temperature in         the range from −60° C. to −30° C., or     -   C₂F₅H and n-BuLi, preferably in tetrahydrofurane at a         temperature in the range from −78° C. to ambient temperature,         preferably up to 25° C., or     -   R¹CF₂CF₂Br (wherein R¹ is as defined above) and i-PrMgCl.LiCl,         preferably in tetrahydrofurane at a temperature in the range         from −78° C. to ambient temperature, preferably up to 25° C.

In a preferred aspect of the method, n-C₄F₉SO₂N₃ or 4-(CH₃)C₆H₄SO₂N₃ are used as electrophilic azidation reagents.

Preferably, the reaction is performed in an organic solvent, more preferably in a solvent selected from tetrahydrofuran and dimethylformamide.

In a preferred aspect of the method of the present invention, the products R_(F)—N₃ are isolated preferably by distillation, in particular when tetrahydrofuran is used as a solvent, or by distillation after addition of an organic solvent having a boiling point lower than 100° C., preferably tetrahydrofuran, in particular when dimethylformamide is used as a solvent.

A further object of the present invention is the use of compounds of general formula R_(F)—N₃ for the synthesis of N-perfluoroalkyl- or N-polyfluoroalkyl-substituted triazoles of formula 1

wherein R_(F) is as defined above,

-   -   R⁴ is selected from a group consisting of C₁₋₁₀ alkyl, XCH₂CH₂,         COOR³, C(CH₃)₂OH, benzyloxy-C₁₋₄-alkyl, pyridyl, phenyl, and         pyridyl or phenyl substituted by a group selected from C₁₋₁₀         alkyl, F, Cl, Br, I, OR³, NO₂, NH₂, CF₃,         by a cycloaddition reaction of the azide R_(F)—N₃ with alkyne of         formula 2

in the presence of copper(I) catalyst in at a temperature in the range from −30° C. to the boiling point of the reaction mixture.

In one aspect of the method, the reaction leading to compound of formula 1 is preferably carried out in the presence of excess of the azide R_(F)—N₃.

In another embodiment of the method, the reaction leading to compound of formula 1 is preferably carried out in the presence of a catalytic amount (for example, 2-20 mol. %, relative to the amount of the alkyne of formula 2) of copper(II) sulfate and a catalytic amount (for example, 4-40 mol. %, relative to the amount of the alkyne of formula 2) of sodium L-ascorbate or in the presence of a catalytic amount (for example, 0.5-10 mol. %, relative to the amount of the alkyne of formula 2) of copper(I) iodide or a catalytic amount (for example, 0.5-10 mol. %, relative to the amount of the alkyne of formula 2) of copper(I) 3-methylsalicylate.

In a preferred aspect of the method, the reactions leading to compound of formula 1 are preferably performed in one pot, starting from [R_(F)]⁻ and R²—N₃ (one-pot two-step method).

An object of the present invention is the use of compounds of formula R_(F)—N₃ for the synthesis of triazoles of general formula 3

wherein R_(F) and R⁴ are as defined above, by cycloaddition reaction of R_(F)—N₃ with alkyne of general formula 4

and with iodine in the presence of tertiary amine as a base, preferably selected from trimethylamine, N,N-diisopropylethylamine, N,N,N′,N′-tetramethylethylenediamine, tris((1-benzyl-1H-1,2,3-triazolyl)methyl)amine or tris((1-tert-butyl-1H-1,2,3-triazolyl)methyl)amine, at a temperature in the range from −30° C. to the boiling point of the reaction mixture.

In one aspect of the method of the present invention, the reaction leading to compounds 3 is preferably performed in the presence of trimethylamine as a base at ambient temperature.

Preferably, the reactions described in the present invention are performed in an organic solvent, more preferably in a solvent selected from tetrahydrofuran and dimethylformamide.

Another object of the present invention are the following compounds prepared according to the invention:

(i) azidoperfluoroalkanes and azidopolyfluoroalkanes of formula R_(F)—N₃,

-   -   wherein R_(F) is selected from the group consisting of         C_(n)F_(2n+1), C_(n)F_(x)H_(2n+1−x), C_(n)F_(x)X_(2n+1−x) or         R¹CF₂CF₂, wherein n is an integer in the interval from 1 to 10,         x is an integer in the interval from 2 to 20 and     -   X is Cl, Br, or I,     -   R¹ is selected from the group consisting of C₁₋₁₀ alkyl, ArO,         ArS, imidazolyl, benzimidazolyl, or pyrazolyl, wherein Ar is         phenyl or substituted phenyl, and wherein R_(F) is not CF₃;         (ii) triazoles of formula 1

-   -   wherein R_(F) is selected from the group consisting of         C_(n)F_(2n+1), C_(n)F_(x)H_(2n+1−x), C_(n)F_(x)X_(2n+1−x) or         R¹CF₂CF₂, wherein n is an integer in the interval from 1 to 10,         x is an integer in the interval from 2 to 20, and         -   X is Cl, Br, or I,         -   R¹ is selected from the group consisting of C₁₋₁₀ alkyl,             ArO, ArS, imidazolyl, benzimidazolyl, or pyrazolyl, wherein             Ar is phenyl or substituted phenyl;     -   R⁴ is selected from a group consisting of C₁₋₁₀ alkyl, XCH₂CH₂,         COOR³, C(CH₃)₂OH, benzyloxy-C₁₋₄-alkyl, pyridyl, phenyl, and         pyridyl or phenyl substituted by a group selected from C₁₋₁₀         alkyl, F, Cl, Br, I, OR³, NO₂, NH₂, CF₃; wherein R³ is C₁₋₅         alkyl;         (iii) triazoles of general formula 3

-   -   wherein R_(F) is selected from the group consisting of         C_(n)F_(2n+1), C_(n)F_(x)H_(2n+1−x), C_(n)F_(x)X_(2n+1−x) or         R¹CF₂CF₂, wherein n is an integer in the interval from 1 to 10,         x is an integer in the interval from 2 to 20, and         -   X is Cl, Br, or I,         -   R¹ is selected from the group consisting of C₁₋₁₀ alkyl,             ArO, ArS, imidazolyl, benzimidazolyl, or pyrazolyl, wherein             Ar is phenyl or substituted phenyl;     -   R⁴ is selected from a group consisting of C₁₋₁₀ alkyl, XCH₂CH₂,         COOR³, C(CH₃)₂OH, benzyloxy-C₁₋₄-alkyl, pyridyl, phenyl, and         pyridyl or phenyl substituted by a group selected from C₁₋₁₀         alkyl, F, Cl, Br, I, OR³, NO₂, NH₂, CF₃; wherein R³ is C₁₋₅         alkyl.

More preferably, the compounds are selected from:

-   Azidopentafluoroethane, -   1-Azido-1,1,2,2,3,3,3-heptafluoropropane, -   1-Azido-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane, -   (2-Azido-1,1,2,2-tetrafluoroethyl)(phenyl)sulfane, -   1-(2-Azido-1,1,2,2-tetrafluoroethoxy)-4-bromobenzene, -   1-(Pentafluoroethyl)-4-phenyl-H-1,2,3-triazole, -   4-(4-Methoxyphenyl)-1-(pentafluoroethyl)-1H-1,2,3-triazole, -   4-(2-Bromophenyl)-1-(pentafluoroethyl)-1H-1,2,3-triazole, -   3-(1-(Pentafluoroethyl)-1H-1,2,3-triazol-4-yl)pyridine, -   4-Phenyl-1-(trifluoromethyl)-1H-1,2,3-triazole, -   4-(p-Tolyl)-1-(trifluoromethyl)-1H-1,2,3-triazole, -   4-(4-Methoxyphenyl)-1-(trifluoromethyl)-1H-1,2,3-triazole, -   4-(2-Bromophenyl)-1-(trifluoromethyl)-1H-1,2,3-triazole, -   4-(4-Nitrophenyl)-1-(trifluoromethyl)-1H-1,2,3-triazole, -   4-(1-(Trifluoromethyl)-1H-1,2,3-triazol-4-yl)aniline, -   4-Butyl-1-(trifluoromethyl)-1H-1,2,3-triazole, -   Ethyl 1-(trifluoromethyl)-1H-1,2,3-triazol-4-carboxylate, -   2-(1-(Trifluoromethyl)-1H-1,2,3-triazol-4-yl)propan-2-ol, -   (S)-4-(2-(Benzyloxy)propyl)-1-(trifluoromethyl)-1H-1,2,3-triazole, -   1-(Pentafluoroethyl)-4-(p-tolyl)-1H-1,2,3-triazole, -   4-(1-(Pentafluoroethyl)-1H-1,2,3-triazol-4-yl)aniline, -   1-(Pentafluoroethyl)-4-(4-(trifluoromethyl)phenyl)-1H-1,2,3-triazole, -   1-(Perfluoropropyl)-4-phenyl-1H-1,2,3-triazole, -   1-(Perfluorooctyl)-4-phenyl-1H-1,2,3-triazole, -   1-(Perfluoropropyl)-4-(p-tolyl)-1H-1,2,3-triazole, -   4-(4-Methoxyphenyl)-1-(perfluorooctyl)-1H-1,2,3-triazole, -   1-(Trifluoromethyl)-4-(4-(trifluoromethyl)phenyl)-1H-1,2,3-triazole, -   4-(4-Fluorophenyl)-1-(trifluoromethyl)-1H-1,2,3-triazole, -   5-Iodo-1-(pentafluoroethyl)-4-phenyl-1H-1,2,3-triazole and -   4-Phenyl-1-(1,1,2,2-tetrafluoro-2-(phenylthio)ethyl)-1H-1,2,3-triazole.

These compounds are useful as starting compounds for production of medicaments, biologically active materials, and agrochemicals, or as components of medicaments, biologically active materials, and agrochemicals.

EXAMPLES List of Abbreviations

Ac acetyl

br.s. broad signal

d doublet

DMF dimethylformamide

EI electron impact ionization

ESI electrospray ionization

Et ethyl

HRMS high resolution mass spectroscopy

IR infrared spectroscopy

m multiplet

[M]⁺ molecular ion

m.p. melting point

Nf nonaflyl, nonafluorobutansulfonyl

NMR nuclear magnetic resonance

q quartet

rt room temperature

R_(f) retention factor

s singlet

t triplet

THF tetrahydrofuran

TMS trimethylsilyl

Tos p-toluenesulfonyl

The subject-matter of the present invention is further illustrated by the following examples, which should not be construed as not limiting the scope of the invention.

Example 1: Azidotrifluoromethane

In a two-neck round-bottom flask, CsF (3.65 g, 24 mmol) was dried under high vacuum overnight at 120° C. The flask was then cooled to rt and filled with argon. Dry DMF (44 mL) was added, the reaction mixture was stirred and cooled to −60° C. A cold solution of CF₃TMS (3.55 mL, 24 mmol) and TosN₃ (3.07 mL, 20 mmol) in dry DMF (6 mL) was added dropwise over 20 min and then the solution was stirred at −60° C. to −30° C. over 4 h. Cold, dry THF (40 mL) was added and the product was distilled from the reaction mixture (bath temperature max. 120° C., normal pressure) to a flask cooled to −78° C. containing PhCF₃ as an internal standard. The product was obtained as a solution in THF containing TMSF as a side-product and traces of CF₃H. Yield 70-80% based on ¹⁹F NMR. ¹³C NMR (101 MHz, CDCl₃) δ=122.0 (q, ¹J_(C—F)=267.6 Hz); ¹⁹F NMR (376 MHz, CDCl₃) δ=−56.3 (s); HRMS (EI) m/z calculated for CF₃N₃ [M]⁺: 111.0044, found 111.0040.

Example 2: Azidoperfluoroethane

To a Schlenk flask filled with argon, dry THF (40 mL) was added. C₂F₅H (1.71 g, 14.3 mmol) was introduced, the resulting solution was cooled to −78° C. and then a solution of n-BuLi (1.6 mol·l⁻¹, 8.9 mL, 14.3 mmol) in hexanes was added dropwise. The mixture was stirred at −78° C. for 30 min, the color changed from colorless to bright yellow. A solution of TosN₃ (2.2 mL, 14.3 mmol) in dry THF (9.5 mL) was added dropwise and a pink precipitate formed. The mixture was stirred for another 30 min at −78° C. and then the product was distilled together with THF at temperature up to 33° C. and pressure 120 torr to a flask cooled to −78° C. containing PhCF₃ as an internal standard. The product was obtained as a solution in THF. Yield 83% based on ¹⁹F NMR. ¹³C NMR (101 MHz, CDCl₃) δ=117.0 (qt, ¹J_(C—F)=267.6 Hz, ²J_(C—F)=41.9 Hz, CF₃), 113.2 (tq, ¹J_(C—F)=272.9 Hz, ²J_(C—F)=41.4 Hz, CF₂); ¹⁹F NMR (376 MHz, CDCl₃) δ=−85.9 (s, 3F), −93.6 (s, 2F); HRMS (EI) m/z calculated for C₂F₅N₃ [M]⁺: 161.0012, found 161.0010.

Example 3: 1-Azido-1,1,2,2,3,3,3-heptafluoropropane

In a screw-cap vial, CsF (0.25 g, 1.66 mmol) was dried under high vacuum at 135° C. for 48 h. The vial was then cooled to ambient temperature and filled with argon. Dry DMF (1.0 mL) was added and the mixture was cooled to −60° C. A cold solution of n-C₃F₇TMS (0.284 mL, 1.4 mmol) and NfN₃ (0.455 g, 1.4 mmol) in dry DMF (0.5 mL) was added over 10 min and then the mixture was stirred at −60° C. to −30° C. for 4 h. Cold and dry THF (2.0 mL) was added and the product was distilled from the reaction mixture (bath temperature max. 95° C.) to a flask cooled to −78° C. containing PhCF₃ as an internal standard. The product was obtained as a THF solution containing TMSF as a side-product. Yield 49-52% according to ¹⁹F NMR. ¹³C NMR (101 MHz, CDCl₃) δ=117.1 (qt, ¹J_(C—F)=287.0 Hz, ²J_(C—F)=33.3 Hz, CF₃); 114.6 (tt, ¹J_(C—F)=275.7 Hz, ²J_(C—F)=30.3 Hz, CF₂); 107.5 (tqt, ¹J_(C—F)=267.7 Hz, ²J_(C—F)=39.4 Hz, ³J_(C—F)=11.1 Hz, CF₂); ¹⁹F NMR (376 MHz, CDCl₃) δ=−80.9 (s, 3F), −89.1 (s, 2F), −128.3 (s, 2F); HRMS (EI) m/z calculated for C₃F₆N₃ [M−F]⁺: 191.9994, found 191.9996.

Example 4: 1-Azido-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane

In a screw-cap vial, CsF (0.25 g, 1.66 mmol) was dried under high vacuum at 135° C. for 48 h.

The vial was then cooled to ambient temperature and filled with argon. Dry DMF (1.0 mL) was added and the mixture was cooled to −60° C. A cold solution of n-C₈F₁₇TMS (0.474 mL, 1.4 mmol) in dry DMF (0.5 mL) was added dropwise over 10 min and the reaction mixture was degased (one freeze-thaw cycle). A solution of NfN₃ (0.455 g, 1.4 mmol) in dry DMF (0.5 mL) was added dropwise and the mixture was stirred from −60° C. to −30° C. for 4 h. Dry cold THF (2.0 mL) was added and the product was distilled from the reaction mixture together with THF (bath max. 90° C.) to a flask cooled to −78° C. containing PhCF₃ as an internal standard. The product was obtained as a solid, which at temperature lower than −60° C. separated from THF. Yield 50-60% according to ¹⁹F NMR. ¹³C NMR (101 MHz, CDCl₃) δ=117.1 (qt, ¹J_(C—F)=311.1 Hz, ²J_(C—F)=32.3 Hz, CF₃); 115.9 (tt, ¹J_(C—F)=292.9 Hz, ²J_(C—F)=33.3 Hz, CF₂ (1)); 113.5-105.1 (m, CF₂ (2-7)); ¹⁹F NMR (376 MHz, CDCl₃) δ=−81.3 (s, 3F), −88.6 (s, 2F), −121.6 (s, 2F), −122.4 (s, 2F), −123.2 (s, 2F), −124.4 (s, 2F), −126.3 (s, 2F), −126.6 (s, 2F). HRMS (EI) m/z calculated for C₈F₁₆N₃ [M−F]⁺: 441.9837, found 441.9836.

Example 5: (2-Azido-1,1,2,2-tetrafluoroethyl)(phenyl)sulfane

i-PrMgCl.LiCl (1.3 mol·l⁻¹, 0.52 mL, 0.675 mmol) was added dropwise to a solution of (2-bromo-1,1,2,2-tetrafluoroethyl)(phenyl)sulfane (150 mg, 0.52 mmol) in dry THF (2 mL) at −78° C. The mixture was stirred for 5 min under argon and then a solution of NfN₃ (0.337 g, 1.038 mmol) in THF (1 mL) was added. The reaction mixture was stirred at −78° C. for 20 min and then at rt for 18 h. A saturated aqueous solution of NH₄Cl (6 mL) was added, the product was extracted to Et₂O (3×10 mL), the combined organic phase was dried with MgSO₄ and evaporated under reduced pressure. Purification on column chromatography (silicagel) gave product as a colorless oil. Yield 53%; IR (CHCl₃, film) ν=2155, 1583, 1578, 1476, 1443, 1299, 1240, 1183, 1115, 1099, 1088, 1025, 892, 750, 690 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ=7.72-7.63 (m, 2H), 7.56-7.48 (m, 1H), 7.48-7.42 (m, 2H); ¹³C NMR (101 MHz, CDCl₃) δ=137.2, 130.9, 129.4, 123.3 (t, J_(C—F)=2.6 Hz), 122.5 (tt, ¹J_(C—F)=290.5 Hz, ²J_(C—F)=39.1 Hz, CF₂), 116.4 (tt, ¹J_(C—F)=274.3 Hz, ²J_(C—F)=34.2 Hz, CF₂); ¹⁹F NMR (376 MHz, CDCl₃) δ=−89.7 (t, ²J_(F—F)=7.4 Hz, 2F), −89.8 (t, ²J_(F—F)=7.4 Hz, 2F).

Example 6: 1-(2-Azido-1,1,2,2-tetrafluoroethoxy)-4-bromobenzene

i-PrMgCl.LiCl (1.3 mol·l⁻¹, 0.46 mL, 0.60 mmol) was added dropwise to the solution of 1-bromo-4-(2-bromo-1,1,2,2-tetrafluoroethoxy)benzene (200 mg, 0.57 mmol) in dry THF (2 mL) at −78° C. The mixture was stirred for 5 min under argon and then a solution of NfN₃ (0.370 g, 1.14 mmol) in THF (1 mL) was added dropwise. The reaction mixture was stirred at −78° C. to 25° C. for 3 h. Saturated aqueous NH₄Cl (6 mL) was added, the product was extracted into Et₂O (3×10 mL), the combined organic phase was dried MgSO₄ and solvent removed under reduced pressure. Purification by column chromatography (silicagel) gave the product as a colorless oil. Yield 71%; R_(f) (hexane)=0.85; IR (CHCl₃, film) ν=2962, 2928, 2158, 1484, 1356, 1296, 1192, 1165, 1110, 1069, 1027, 956, 825, 781 cm⁻¹; ¹H NMR (300.13 MHz, CDCl₃) δ=7.11 (m, 2H), 7.52 (m, 2H); ¹³C NMR (75.48 MHz, CDCl₃) δ=114.2 (tt, ¹J_(C—F)=272 Hz, ²J_(C—F)=40.0 Hz, CF₂), 116.0 (tt, ¹J_(C—F)=276 Hz, ²J_(C—F)=38.5 Hz, CF₂), 120.2, 123.4 (t, ⁴J_(C—F)=0.9 Hz), 132.9, 147.7 (t, ³J_(C—F)=1.7 Hz); ¹⁹F NMR (282.38 MHz, CDCl₃) δ=−94.0 (t, ³J_(F—F)=2.7 Hz, 2F), −87.4 (t, ³J_(F—F)=2.7 Hz, 2F).

Example 7: 1-(Pentafluoroethyl)-4-phenyl-1H-1,2,3-triazole

To a 10 mL screw cap vial, phenylacetylene (0.5 mmol) and a solution of azidopentafluoroethane in THF (˜0.60 mmol, 3-4 mL) were added. An aqueous solution of CuSO₄.5H₂O (1 mol·l⁻¹, 0.05 mmol, 50 μl) and sodium L-ascorbate (1 mol·l⁻¹, 0.05 mmol, 50 μl) were added, the vial was closed and the content was stirred at rt for 18 h. Saturated aqueous NH₄Cl (10 mL) was added and the product was extracted into CH₂Cl₂ (3×10 mL). The combined organic phase was washed with water (2×10 mL), dried (MgSO₄), filtered and solvent was removed under reduced pressure. Purification by column chromatography (silicagel) gave pure product as a white solid. Yield 84%; m.p. 82-83° C.; R_(f) (cyklohexane:EtOAc 97:3)=0.28; IR (CHCl₃, film) ν=1216, 1172, 1120, 1075, 691 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ=8.13 (s, 1H), 7.90-7.86 (m, 2H), 7.51-7.46 (m, 2H), 7.45-7.40 (m, 1H); ¹³C NMR (101 MHz, CDCl₃) δ=148.9, 129.5, 129.2, 128.6, 126.3, 117.9, 117.2 (qt, ¹J_(C—F)=287.6 Hz, ²J_(C—F)=41.3 Hz, CF₃), 110.4 (tq, ¹J_(C—F)=270.9 Hz, ²J_(C—F)=43.1 Hz, CF₂); ¹⁹F NMR (376 MHz, CDCl₃) δ=−84.4 (s, 3F), −99.2 (s, 2F); HRMS (ESI) m/z calculated for C₁₀H₇N₃F₅ [M+H]⁺: 264.0555, found 264.0555.

Example 8: 4-(4-Methoxyphenyl)-1-(pentafluoroethyl)-1H-1,2,3-triazole

To a 10 mL screw cap vial, 4-methoxyphenylacetylene (0.5 mmol) and a solution of azidopentafluoroethane in THF (˜0.60 mmol, 3-4 mL) were added. An aqueous solution of CuSO₄.5H₂O (1 mol·l⁻¹, 0.05 mmol, 50 μl) and sodium L-ascorbate (1 mol·l⁻¹, 0.05 mmol, 50 μl) were added, the vial was closed and the content was stirred at rt for 18 h. Saturated aqueous NH₄Cl (10 mL) was added and the product was extracted into CH₂Cl₂ (3×10 mL).

The combined organic phase was washed with water (2×10 mL), dried (MgSO₄), filtered and solvent was removed under reduced pressure. Purification by column chromatography (silicagel) gave pure product as a white solid. Yield 63%; m.p. 100-102° C.; R_(f) (cyklohexane:EtOAc, 95:5)=0.26; IR (CHCl₃, film) ν=1618, 1501, 1434, 1223, 1123, 536 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ=8.04 (s, 1H), 7.82-7.78 (m, 2H), 7.01-6.97 (m, 2H), 3.86 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ=160.6, 148.7, 127.7, 121.2, 117.2 (qt, ¹J_(C—F)=287.5 Hz, ²J_(C—F)=41.4 Hz, CF₃), 116.9, 114.6, 110.3 (tq, ¹J_(C—F)=270.6 Hz, ²J_(C—F)=43.1 Hz, CF₂), 55.5; ¹⁹F NMR (376 MHz, CDCl₃) δ=−84.4 (s, 3F), −99.2 (s, 2F); HRMS (ESI) m/z calculated for C₁₁H₉ON₃F₅ [M+H]⁺: 294.0660, found 294.0661.

Example 9: 4-(2-Bromophenyl)-1-(pentafluoroethyl)-1H-1,2,3-triazole

To a 10 mL screw cap vial, 2-bromophenylacetylene (0.5 mmol) and a solution of azidopentafluoroethane in THF (˜0.60 mmol, 3-4 mL) were added. An aqueous solution of CuSO₄.5H₂O (1 mol·l⁻¹, 0.05 mmol, 50 μl) and sodium L-ascorbate (1 mol·l⁻¹, 0.05 mmol, 50 μl) were added, the vial was closed and the content was stirred at rt for 18 h. Saturated aqueous NH₄Cl (10 mL) was added and the product was extracted into CH₂Cl₂ (3×10 mL). The combined organic phase was washed with water (2×10 mL), dried (MgSO₄), filtered and solvent was removed under reduced pressure. Purification by column chromatography (silicagel) gave pure product as a white solid. Yield 37%; R_(f) (cyklohexane:EtOAc 95:5)=0.53; IR (CHCl₃, film) ν=1430, 1210, 1128, 1077, 972 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ=8.63 (s, 1H), 8.15 (dd, J=7.8, 1.7 Hz, 1H), 7.70 (dd, J=8.1, 1.2 Hz, 1H), 7.47 (td, J=7.6, 1.3 Hz, 1H), 7.29 (td, 1H); ¹³C NMR (101 MHz, CDCl₃) δ=146.4, 133.9, 131.1, 130.6, 129.4, 128.1, 121.6, 121.4, 117.2 (qt, ¹J_(C—F)=287.5 Hz, ²J_(C—F)=41.2 Hz, CF₃), 110.3 (tq, ¹J_(C—F)=271.4 Hz, ¹J_(C—F)=43.2 Hz, CF₂); ¹⁹F NMR (376 MHz, CDCl₃) δ=−84.4 (s, 3F), −99.2 (s, 2F); HRMS (ESI) m/z calculated for C₁₀H₆N₃BrF₅ [M+H]⁺: 341.9660, found 341.9661.

Example 10: 3-(1-(Pentafluorethyl)-1H-1,2,3-triazol-4-yl)pyridine

To a 10 mL screw cap vial, 3-pyridylacetylene (0.5 mmol) and a solution of azidopentafluoroethane in THF (˜0.60 mmol, 3-4 mL) were added. An aqueous solution of CuSO₄.5H₂O (1 mol·l⁻¹, 0.05 mmol, 50 μl) and sodium L-ascorbate (1 mol·l⁻¹, 0.05 mmol, 50 μl) were added, the vial was closed and the content was stirred at rt for 18 h. Saturated aqueous NH₄Cl (10 mL) was added and the product was extracted into CH₂Cl₂ (3×10 mL). The combined organic phase was washed with water (2×10 mL), dried (MgSO₄), filtered and solvent was removed under reduced pressure. Purification by column chromatography (silicagel) gave pure product as a white solid. Yield 38%; m.p. 120-122° C.; R_(f) (cyklohexane:EtOAc 1:1)=0.48; IR (CHCl₃, film) ν=1578, 1439, 1218, 1169, 1121, 1078 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ=9.09 (d, J=2.5 Hz, 1H), 8.68 (dd, J=4.9, 1.6 Hz, 1H), 8.29 (s, 1H), 8.27 (dt, J=8.0, 2.0 Hz, 1H), 7.45 (dd, J=8.0, 4.9 Hz, 1H); ¹³C NMR (101 MHz, CDCl₃) δ=150.5, 147.4, 145.9, 133.7, 124.9, 124.0, 118.5, 117.1 (qt, ¹J_(C—F)=287.5 Hz, ²J_(C—F)=40.6 Hz, CF₃), 110.3 (tq, ¹J_(C—F)=272.2 Hz, ²J_(C—F)=43.1 Hz, CF₂); ¹⁹F NMR (376 MHz, CDCl₃) δ=−84.3 (s, 3F), −99.1 (s, 2F); HRMS (ESI) m/z calculated for C₉H₆N₄F₅ [M+H+]: 265.0507, found 265.0508.

Example 11: 4-Phenyl-1-(trifluoromethyl)-1H-1,2,3-triazole

To a 10 mL screw cap vial, copper(I) 3-methylsalicylate (5.4 mg, 0.025 mmol), a cold (−20° C.) solution of azidotrifluoromethane in THF (˜1.5 mmol, 3-4 mL) and a solution of phenylacetylene (1.0 mmol) in THF (0.5 mL) were added. The vial was closed and the content stirred at rt for 18 h. THF was removed under reduced pressure, Et₂O (20 mL) was added and the organic phase was washed with aqueous NaHCO₃ (5%, 2×10 mL), water (10 mL), aqueous LiCl (1 mol·l⁻¹, 10 mL) and brine (10 mL), dried (MgSO₄), filtered and solvent was removed under reduced pressure. Purification by column chromatography (silicagel) gave the product as a white solid. Yield 81%; m.p. 91-92° C.; R_(f) (cyklohexane:EtOAc, 97:3)=0.27; IR (CHCl₃, film) ν=1430, 1205, 1006, 694 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ=8.14 (s, 1H), 7.89-7.86 (m, 2H), 7.50-7.46 (m, 2H), 7.44-7.40 (m, 1H); ¹³C NMR (101 MHz, CDCl₃) δ=148.6, 129.4, 129.2, 128.6, 126.2, 117.7 (q, ¹J_(C—F)=267.7 Hz, CF₃), 117.3; ¹⁹F NMR (376 MHz, CDCl₃) δ=−59.3 (s); HRMS (EI) m/z calculated for C₉H₆N₃F₃ [M]⁺: 213.0514, found 213.0520.

Example 12: 4-(p-Tolyl)-1-(trifluoromethyl)-1H-1,2,3-triazole

To a 10 mL screw cap vial, copper(I) 3-methylsalicylate (5.4 mg, 0.025 mmol), a cold (−20° C.) solution of azidotrifluoromethane in THF (˜1.5 mmol, 3-4 mL) and a solution of 4-methylphenylacetylene (1.0 mmol) in THF (0.5 mL) were added. The vial was closed and the content stirred at rt for 18 h. THF was removed under reduced pressure, Et₂O (20 mL) was added and the organic phase was washed with aqueous NaHCO₃ (5%, 2×10 mL), water (10 mL), aqueous LiCl (1 mol·l⁻¹, 10 mL) and brine (10 mL), dried (MgSO₄), filtered and solvent was removed under reduced pressure. Purification by column chromatography (silicagel) gave the product as a white solid. Yield 79%; m.p. 99-101° C.; R_(f) (cyklohexane:EtOAc, 97:3)=0.19; IR (CHCl₃, film)=1444, 1189, 1007, 814 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ=8.09 (s, 1H), 7.77-7.74 (m, 2H), 7.30-7.27 (m, 2H), 2.41 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ=148.7, 139.5, 129.8, 126.1, 125.8, 117.7 (q, ¹J_(C—F)=268.1 Hz, CF₃), 116.8, 21.4; ¹⁹F NMR (376 MHz, CDCl₃) δ=−59.3 (s); HRMS (ESI) m/z calculated for C₁₀H₉N₃F₃ [M+H]+: 228.0743, found 228.0742.

Example 13: 4-(4-Methoxyphenyl)-1-(trifluoromethyl)-1H-1,2,3-triazole

To a 10 mL screw cap vial, copper(I) 3-methylsalicylate (5.4 mg, 0.025 mmol), a cold (−20° C.) solution of azidotrifluoromethane in THF (˜1.5 mmol, 3-4 mL) and a solution of 4-methoxyphenylacetylene (1.0 mmol) in THF (0.5 mL) were added. The vial was closed and the content stirred at rt for 18 h. THF was removed under reduced pressure, Et₂O (20 mL) was added and the organic phase was washed with aqueous NaHCO₃ (5%, 2×10 mL), water (10 mL), aqueous LiCl (1 mol·l⁻¹, 10 mL) and brine (10 mL), dried (MgSO₄), filtered and solvent was removed under reduced pressure. Purification by column chromatography (silicagel) gave the product as a white solid. Yield 79%; m.p. 112-115° C.; R_(f) (cyklohexane:EtOAc, 97:3)=0.12; IR (CHCl₃, film)=1445, 1257, 1215, 1194, 828 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ=8.04 (s, 1H), 7.82-7.78 (m, 2H), 7.02-6.98 (m, 2H), 3.86 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ=160.5, 148.5, 127.6, 121.2, 117.8 (q, ¹J_(C—F)=268.0 Hz, CF₃), 116.3, 114.6, 55.5 (s); ¹⁹F NMR (376 MHz, CDCl₃) δ=−59.4 (s); HRMS (ESI) m/z calculated for C₁₀H₉N₃OF₃ [M+H]⁺: 244.0692, found 244.0693.

Example 14: 4-(2-Bromophenyl)-1-(trifluoromethyl)-1H-1,2,3-triazole

To a 10 mL screw cap vial, copper(I) 3-methylsalicylate (5.4 mg, 0.025 mmol), a cold (−20° C.) solution of azidotrifluoromethane in THF (˜1.5 mmol, 3-4 mL) and a solution of 2-bromophenylacetylene (1.0 mmol) in THF (0.5 mL) were added. The vial was closed and the content stirred at rt for 18 h. THF was removed under reduced pressure, Et₂O (20 mL) was added and the organic phase was washed with aqueous NaHCO₃ (5%, 2×10 mL), water (10 mL), aqueous LiCl (1 mol·l⁻¹, 10 mL) and brine (10 mL), dried (MgSO₄), filtered and solvent was removed under reduced pressure. Purification by column chromatography (silicagel) gave the product as a yellow oil. Yield 84%; R_(f) (cyklohexane:EtOAc, 97:3)=0.27; IR (CHCl₃, film)=1420, 1206, 1191, 760 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ=8.63 (s, 1H), 8.16-8.14 (ddd, J=7.8, 1.7, 0.4 Hz, 1H), 7.71-7.69 (ddd, J=8.1, 1.3, 0.4 Hz, 1H), 7.49-7.45 (ddd, J=7.9, 7.4, 1.3 Hz, 1H), 7.31-7.27 (ddd, J=8.1, 7.4, 1.8 Hz, 1H); ¹³C NMR (101 MHz, CDCl₃) δ=146.1, 133.8, 131.0, 130.5, 129.4, 128.0, 121.4, 120.6, 117.7 (q, ¹J_(C—F)=268.4 Hz); ¹⁹F NMR (376 MHz, CDCl₃) δ=−59.2 (s); HRMS (ESI) m/z calculated for C₉H₆N₃F₃Br [M+H]⁺: 291.9692, found 291.9692.

Example 15: 4-(4-Nitrophenyl)-1-(trifluoromethyl)-1H-1,2,3-triazole

To a 10 mL screw cap vial, copper(I) 3-methylsalicylate (5.4 mg, 0.025 mmol), a cold (−20° C.) solution of azidotrifluoromethane in THF (˜1.5 mmol, 3-4 mL) and a solution of 2-nitrophenylacetylene (1.0 mmol) in THF (0.5 mL) were added. The vial was closed and the content stirred at rt for 18 h. THF was removed under reduced pressure, Et₂O (20 mL) was added and the organic phase was washed with aqueous NaHCO₃ (5%, 2×10 mL), water (10 mL), aqueous LiCl (1 mol·l⁻¹, 10 mL) and brine (10 mL), dried (MgSO₄), filtered and solvent was removed under reduced pressure. Purification by column chromatography (silicagel) gave the product as a yellow solid. Yield 82%; m.p. 166-168° C.; R_(f) (cyklohexane:EtOAc, 97:3)=0.25; IR (CHCl₃, film)=1518, 1350, 1217, 1002 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ=8.38-8.34 (m, 2H), 8.31 (s, 1H), 8.10-8.06 (m, 2H); ¹³C NMR (101 MHz, CDCl₃) δ=148.3, 146.4, 134.8, 127.0, 124.6, 118.9, 117.6 (q, ¹J_(C—F)=269.1 Hz); ¹⁹F NMR (376 MHz, CDCl₃) δ=−59.3 (s); HRMS (CI) m/z calculated for C₉H₆N₄O₂F₃ [M+H]⁺: 259.0437, found 259.0439.

Example 16: 4-(1-(Trifluoromethyl)-1H-1,2,3-triazol-4-yl)aniline

To a 10 mL screw cap vial, copper(I) 3-methylsalicylate (5.4 mg, 0.025 mmol), a cold (−20° C.) solution of azidotrifluoromethane in THF (˜1.5 mmol, 3-4 mL) and a solution of 4-ethynylaniline (1.0 mmol) in THF (0.5 mL) were added. The vial was closed and the content stirred at rt for 18 h. THF was removed under reduced pressure, Et₂O (20 mL) was added and the organic phase was washed with aqueous NaHCO₃ (5%, 2×10 mL), water (10 mL), aqueous LiCl (1 mol·l⁻¹, 10 mL) and brine (10 mL), dried (MgSO₄), filtered and solvent was removed under reduced pressure. Purification by column chromatography (silicagel) gave the product as a yellow solid. Yield 76%; m.p. 104-106° C.; R_(f) (cyklohexane:EtOAc:Et₃N, 80:19:1)=0.14; IR (CHCl₃, film) ν=3398, 3321, 1432, 1195, 819 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ=7.98 (s, 1H), 7.67-7.64 (m, 2H), 6.77-6.73 (m, 2H), 3.86 (br s, 2H); ¹³C NMR (101 MHz, CDCl₃) δ=149.0, 147.7, 127.5, 118.7, 117.7 (q, ¹J_(C—F)=267.7 Hz), 115.6, 115.2; ¹⁹F NMR (376 MHz, CDCl₃) δ=−59.4 (s); HRMS (ESI) m/z calculated for C₉H₈N₄F₃ [M+H]⁺: 229.0696, found 229.0696.

Example 17: 4-Butyl-1-(trifluoromethyl)-1H-1,2,3-triazole

To a 10 mL screw cap vial, copper(I) 3-methylsalicylate (5.4 mg, 0.025 mmol), a cold (−20° C.) solution of azidotrifluoromethane in THF (˜1.5 mmol, 3-4 mL) and a solution of hex-1-yne (1.0 mmol) in THF (0.5 mL) were added. The vial was closed and the content stirred at rt for 18 h. THF was removed under reduced pressure, Et₂O (20 mL) was added and the organic phase was washed with aqueous NaHCO₃ (5%, 2×10 mL), water (10 mL), aqueous LiCl (1 mol·l⁻¹, 10 mL) and brine (10 mL), dried (MgSO₄), filtered and solvent was removed under reduced pressure. Purification by column chromatography (silicagel) gave the product as a yellow oil. Yield 24%; R_(f) (cyklohexane:EtOAc, 80:19:1)=0.17; IR (CHCl₃, film) ν=2938, 1382, 1194, 974 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ=7.69 (s, 1H), 2.79 (d, J=7.7 Hz, 2H), 1.70 (dt, J=15.4, 7.5 Hz, 2H), 1.41 (dq, J=14.7, 7.4 Hz, 2H), 0.95 (t, J=7.4 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ=149.4, 118.5, 117.7 (q, ¹J_(C—F)=267.3 Hz), 31.1, 25.0, 22.3, 13.8; ¹⁹F NMR (376 MHz, CDCl₃) δ=−59.4 (s); HRMS (EI) m/z calculated for C₇H₁₀N₃F₃ [M]⁺: 193.0827, found 193.0828.

Example 18: Ethyl 1-(trifluoromethyl)-1H-1,2,3-triazole-4-carboxylate

To a 10 mL screw cap vial, copper(I) 3-methylsalicylate (5.4 mg, 0.025 mmol), a cold (−20° C.) solution of azidotrifluoromethane in THF (˜1.5 mmol, 3-4 mL) and a solution of ethyl propiolate (1.0 mmol) in THF (0.5 mL) were added. The vial was closed and the content stirred at rt for 18 h. THF was removed under reduced pressure, Et₂O (20 mL) was added and the organic phase was washed with aqueous NaHCO₃ (5%, 2×10 mL), water (10 mL), aqueous LiCl (1 mol·l⁻¹, 10 mL) and brine (10 mL), dried (MgSO₄), filtered and solvent was removed under reduced pressure. Purification by column chromatography (silicagel) gave the product as a yellow oil. Yield 48%; R_(f) (cyklohexane:EtOAc, 95:5)=0.12; IR (CHCl₃, film) ν=1744, 1444, 1266, 1222 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ=8.53 (s, 1H), 4.48 (q, J=7.1 Hz, 2H), 1.43 (t, J=7.1 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ=159.3, 140.9, 125.8, 117.4 (q, ¹J_(C—F)=269.8 Hz), 62.2, 14.3; ¹⁹F NMR (376 MHz, CDCl₃) δ=−59.3 (s); HRMS (ESI) m/z vypočteno pro C₆H₇N₃O₂F₃ [M+H]⁺: 210.0485, nalezeno 210.0485, calculated for C₆H₆N₃O₂F₃Na [M+Na]⁺: 232.0304, found 232.0304.

Example 19: 2-(1-(Trifluoromethyl)-1H-1,2,3-triazol-4-yl)propan-2-ol

To a 10 mL screw cap vial, copper(I) 3-methylsalicylate (5.4 mg, 0.025 mmol), a cold (−20° C.) solution of azidotrifluoromethane in THF (˜1.5 mmol, 3-4 mL) and a solution of 2-methylbut-3-yn-2-ol (1.0 mmol) in THF (0.5 mL) were added. The vial was closed and the content stirred at rt for 18 h. THF was removed under reduced pressure, Et₂O (20 mL) was added and the organic phase was washed with aqueous NaHCO₃ (5%, 2×10 mL), water (10 mL), aqueous LiCl (1 mol·l⁻¹, 10 mL) and brine (10 mL), dried (MgSO₄), filtered and solvent was removed under reduced pressure. Purification by column chromatography (silicagel) gave the product as a white solid. Yield 74%; m.p. 42-43° C.; R_(f) (cyklohexane:EtOAc, 70:30)=0.21; IR (CHCl₃, film) ν=3401, 1435, 1191, 982 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ=7.90 (s, 1H), 2.9 (s, 1H), 1.69 (s, 6H); ¹³C NMR (101 MHz, CDCl₃) δ=156.8, 117.9, 117.7 (q, ¹J_(C—F)=268.2 Hz), 68.7, 30.4; ¹⁹F NMR (376 MHz, CDCl₃) δ=−59.3 (s); HRMS (EI) m/z calculated for C₆H₈N₃OF₃Na [M+Na]⁺: 218.0512, found 218.0511.

Example 20: (S)-4-(2-(Benzyloxy)propyl)-1-(trifluoromethyl)-1H-1,2,3-triazole

To a 10 mL screw cap vial, copper(I) 3-methylsalicylate (5.4 mg, 0.025 mmol), a cold (−20° C.) solution of azidotrifluoromethane in THF (˜1.5 mmol, 3-4 mL) and a solution of (S)-((pent-4-yn-2-yloxy)methyl)benzene (1.0 mmol) in THF (0.5 mL) were added. The vial was closed and the content stirred at rt for 18 h. THF was removed under reduced pressure, Et₂O (20 mL) was added and the organic phase was washed with aqueous NaHCO₃ (5%, 2×10 mL), water (10 mL), aqueous LiCl (1 mol·l⁻¹, 10 mL) and brine (10 mL), dried (MgSO₄), filtered and solvent was removed under reduced pressure. Purification by column chromatography (silicagel) gave the product as a pale yellow oil. Yield 90%; R_(f) (cyklohexane:EtOAc, 95:5)=0.09; IR (CHCl₃, film) ν=1440, 1278, 1207, 980 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ=7.71 (s, 1H), 7.34-7.27 (m, 3H), 7.26-7.22 (m, 2H), 4.61 (d, J=11.6 Hz, 1H), 4.41 (d, J=11.6 Hz, 1H), 3.92-3.85 (m, 1H), 3.02 (dd, J=15.0, 4.7 Hz, 1H), 2.96 (dd, J=15.0, 7.0 Hz, 1H), 1.28 (d, J=6.1 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ=145.9, 138.4, 128.5, 127.8, 120.3, 117.7 (q, ¹J_(C—F)=267.9 Hz), 73.6, 70.8, 32.8, 19.5; ¹⁹F NMR (376 MHz, CDCl₃) δ=−59.4 (s); HRMS (ESI) m/z calculated for C₁₃H₁₅N₃₀F₃ [M+H]+: 286.1162, nalezeno 286.1162, calculated for [M+Na]⁺: 308.0981, found 308.0983.

Example 21: 1-(Pentafluoroethyl)-4-(p-tolyl)-1H-1,2,3-triazole

To a 10 mL screw cap vial, copper(I) 3-methylsalicylate (5.4 mg, 0.025 mmol), a cold (−20° C.) solution of azidopentafluoroethane in THF (˜1.5 mmol, 3-4 mL) and a solution of p-tolylacetylene (1.0 mmol) in THF (0.5 mL) were added. The vial was closed and the content stirred at rt for 18 h. THF was removed under reduced pressure, Et₂O (20 mL) was added and the organic phase was washed with aqueous NaHCO₃ (5%, 2×10 mL), water (10 mL), aqueous LiCl (1 mol·l⁻¹, 10 mL) and brine (10 mL), dried (MgSO₄), filtered and solvent was removed under reduced pressure. Purification by column chromatography (silicagel) gave the product as a white solid. Yield 88%; m.p. 92-94° C.; IR (CHCl₃, film) ν=1219, 1175, 1122, 1075, 736 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ=8.09 (s, 1H), 7.77-7.74 (m, 2H), 7.30-7.27 (m, 2H), 2.41 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ=149.0, 139.6, 129.9, 126.2, 125.8, 117.5, 117.2 (qt, ¹J_(C—F)=287.9 Hz, ²J_(C—F)=41.4 Hz, CF₃), 110.3 (tq, ¹J_(C—F)=270.7 Hz, ²J_(C—F)=41.4 Hz, CF₂), 21.5; ¹⁹F NMR (376 MHz, CDCl₃) δ=−84.4 (s, 3F), −99.2 (s, 2F); HRMS (EI⁺) m/z calculated for C₁₁H₈N₃F₅ [M]⁺: 277.0638, found 277.0639.

Example 22: 4-(1-(Pentafluoroethyl)-1H-1,2,3-triazol-4-yl)aniline

To a 10 mL screw cap vial, copper(I) 3-methylsalicylate (5.4 mg, 0.025 mmol), a cold (−20° C.) solution of azidopentafluoroethane in THF (˜1.5 mmol, 3-4 mL) and a solution of 4-ethynylaniline (1.0 mmol) in THF (0.5 mL) were added. The vial was closed and the content stirred at rt for 18 h. THF was removed under reduced pressure, Et₂O (20 mL) was added and the organic phase was washed with aqueous NaHCO₃ (5%, 2×10 mL), water (10 mL), aqueous LiCl (1 mol·l⁻¹, 10 mL) and brine (10 mL), dried (MgSO₄), filtered and solvent was removed under reduced pressure. Purification by column chromatography (silicagel) gave the product as a yellow solid. Yield 97%; m.p. 86-89° C.; IR (CHCl₃, film) ν=1625, 1353, 1217, 1185, 1123, 1074, 755 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ=8.00 (s, 1H), 7.70-7.68 (m, 2H), 6.79-6.77 (m, 2H), 3.92 (br s, 2H); ¹³C NMR (101 MHz, CDCl₃) δ=149.2, 147.6, 127.6, 118.7, 117.4 (qt, ¹J_(C—F)=287.3 Hz, ²J_(C—F)=41.5 Hz, CF₃), 116.0, 115.4, 110.3 (tq, ¹J_(C—F)=270.1 Hz, ²J_(C—F)=42.8 Hz, CF₂); ¹⁹F NMR (376 MHz, CDCl₃) δ=−84.4 (s, 3F), −99.2 (s, 2F); HRMS (ESI) m/z calculated for C₁₀H₈N₄F₅ [M+H]⁺: 279.06636, found 279.06641.

Example 23: 1-(Pentafluoroethyl)-4-(4-(trifluoromethyl)phenyl)-1H-1,2,3-triazole

To a 10 mL screw cap vial, copper(I) 3-methylsalicylate (5.4 mg, 0.025 mmol), a cold (−20° C.) solution of azidopentafluoroethane in THF (˜1.5 mmol, 3-4 mL) and a solution of (4-trifluoromethyl)phenylacetylene (1.0 mmol) in THF (0.5 mL) were added. The vial was closed and the content stirred at rt for 18 h. THF was removed under reduced pressure, Et₂O (20 mL) was added and the organic phase was washed with aqueous NaHCO₃ (5%, 2×10 mL), water (10 mL), aqueous LiCl (1 mol·l⁻¹, 10 mL) and brine (10 mL), dried (MgSO₄), filtered and solvent was removed under reduced pressure. Purification by column chromatography (silicagel) gave the product as a white solid. Yield 91%; m.p. 121-124° C.; IR (CHCl₃, film) ν=1329, 1218, 1130, 1065, 747 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ=8.24 (s, 1H), 8.02-8.00 (m, 2H), 7.75-7.73 (m, 2H); ¹³C NMR (101 MHz, CDCl₃) δ=147.5, 132.0, 131.5 (q, ²J_(C—F)=33.3 Hz), 126.6, 126.3 (q, ³J_(C—F)=3.0 Hz), 124.0 (q, ¹J_(C—F)=272.7 Hz, CF₃), 118.8, 117.1 (qt, ¹J_(C—F)=287.9 Hz, ²J_(C—F)=41.4 Hz, CF₃), 110.3 (tq, ¹J_(C—F)=271.7 Hz, ²J_(C—F)=43.4 Hz, CF₂); ¹⁹F NMR (376 MHz, CDCl₃) δ=−63.3 (s, 3F), −84.4 (s, 3F), −99.2 (s, 2F); HRMS (ESI) m/z calculated for C₁₁H₈N₃F₈ [M]⁺: 331.0356, found 331.0350.

Example 24: 1-(Perfluoropropyl)-4-phenyl-1H-1,2,3-triazole

To a 10 mL screw cap vial, copper(I) 3-methylsalicylate (5.4 mg, 0.025 mmol), a cold (−20° C.) solution of 1-azido-1,1,2,2,3,3,3-heptafluoropropane in THF (˜1.5 mmol, 3-4 mL) and a solution of phenylacetylene (1.0 mmol) in THF (0.5 mL) were added. The vial was closed and the content stirred at rt for 18 h. THF was removed under reduced pressure, Et₂O (20 mL) was added and the organic phase was washed with aqueous NaHCO₃ (5%, 2×10 mL), water (10 mL), aqueous LiCl (1 mol·l⁻¹, 10 mL) and brine (10 mL), dried (MgSO₄), filtered and solvent was removed under reduced pressure. Purification by column chromatography (silicagel) gave the product as a white solid. Yield 41%; m.p. 72-74° C.; IR (CHCl₃, film) ν=1423, 1226, 1196, 1137, 1051, 883, 694 cm⁻¹; ¹H NMR (500 MHz, CDCl₃) δ=8.12 (s, 1H), 7.89-7.87 (m, 2H), 7.50-7.46 (m, 2H), 7.44-7.40 (m, 1H); ¹³C NMR (125.7 MHz, CDCl₃) δ=148.9, 129.6, 129.3, 128.6, 126.3, 118.1, 117.4 (qt, ¹J_(C—F)=295.4 Hz, ²J_(C—F)=32.7 Hz, CF₃); 112.0 (tt, ¹J_(C—F)=272.8 Hz, ²J_(C—F)=32.7 Hz, CF₂); 107.6 (tq, ¹J_(C—F)=264.0 Hz, ²J_(C—F)=40.2 Hz, CF₂); ¹⁹F NMR (376 MHz, CDCl₃) δ=−81.0 (s, 3F), −96.5 (s, 2F), −127.6 (s, 2F); HRMS (EI) m/z calculated for C₁₁H₆N₃F₇ [M]⁺: 313.0450, found 313.0445.

Example 25: 1-(Perfluorooctyl)-4-phenyl-1H-1,2,3-triazole

To a 10 mL screw cap vial, copper(I) 3-methylsalicylate (5.4 mg, 0.025 mmol), a cold (−20° C.) solution of 1-azido-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane in THF (˜1.5 mmol, 3-4 mL) and a solution of phenylacetylene (1.0 mmol) in THF (0.5 mL) were added.

The vial was closed and the content stirred at rt for 18 h. THF was removed under reduced pressure, Et₂O (20 mL) was added and the organic phase was washed with aqueous NaHCO₃ (5%, 2×10 mL), water (10 mL), aqueous LiCl (1 mol·l⁻¹, 10 mL) and brine (10 mL), dried (MgSO₄), filtered and solvent was removed under reduced pressure. Purification by column chromatography (silicagel) gave the product as a white solid. Yield 57%; m.p. 132-133° C.; IR (CHCl₃, film) ν=1218, 1151, 749, 671 cm⁻¹; ¹H NMR (500 MHz, CDCl₃) δ=8.11 (s, 1H), 7.89-7.87 (m, 2H), 7.50-7.47 (m, 2H), 7.44-7.41 (m, 1H); ¹³C NMR (125.7 MHz, CDCl₃) δ=148.8, 129.6, 129.3, 128.6, 126.3, 118.1, 117.2, 112.5, 110.9, 110.82, 110.79, 110.3, 109.8, 108.5; ¹⁹F NMR (470.4 MHz, CDCl₃) δ=−81.2 (t, ³J_(F—F)=9.9 Hz, CF₃), −95.6 (t, ³J_(F—F)=11.0 Hz, CF₂), −121.7 to −122.9 (m, 3×CF₂), −123.0 to −123.3 (m, 2×CF₂), −126.6 (br s, CF₂); HRMS (EI) m/z calculated for C₁₆H₇N₃F₁₇ [M]⁺: 564.03630, found 564.03631.

Example 26: 1-(Perfluoropropyl)-4-(p-tolyl)-1H-1,2,3-triazole

To a 10 mL screw cap vial, copper(I) 3-methylsalicylate (5.4 mg, 0.025 mmol), a cold (−20° C.) solution of 1-azido-1,1,2,2,3,3,3-heptafluoropropane in THF (˜1.5 mmol, 3-4 mL) and a solution of p-tolylacetylene (1.0 mmol) in THF (0.5 mL) were added. The vial was closed and the content stirred at rt for 18 h. THF was removed under reduced pressure, Et₂O (20 mL) was added and the organic phase was washed with aqueous NaHCO₃ (5%, 2×10 mL), water (10 mL), aqueous LiCl (1 mol·l⁻¹, 10 mL) and brine (10 mL), dried (MgSO₄), filtered and solvent was removed under reduced pressure. Purification by column chromatography (silicagel) gave the product as a white solid. Yield 41%; m.p. 86-88° C.; IR (CHCl₃, film) ν=1236, 1139, 882, 750, 671 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ=8.08 (s, 1H), 7.78-7.76 (m, 2H), 7.29-7.27 (m, 2H), 2.41 (s, 1H); ¹³C NMR (101.0 MHz, CDCl₃) δ=148.9, 129.6, 139.6, 129.9, 126.2, 125.8, 117.7, 117.4 (qt, ¹J_(C—F)=287.9 Hz, ²J_(C—F)=28.3 Hz, CF₃); 112.0 (tt, ¹J_(C—F)=273.7 Hz, ²J_(C—F)=32.3 Hz, CF₂); 107.6 (tq, ¹J_(C—F)=269.7 Hz, ²J_(C—F)=40.4 Hz, CF₂), 21.5; ¹⁹F NMR (376 MHz, CDCl₃) δ=−81.0 (s, 3F), −96.5 (s, 2F), −127.7 (s, 2F); HRMS (EI) m/z calculated for C₁₂H₉N₃F₇ [M+H]⁺: 328.06792, found 328.06807.

Example 27: 4-(4-Methoxyphenyl)-1-(perfluorooctyl)-1H-1,2,3-triazole

To a 10 mL screw cap vial, copper(I) 3-methylsalicylate (5.4 mg, 0.025 mmol), a cold (−20° C.) solution of 1-azido-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane in THF (˜1.5 mmol, 3-4 mL) and a solution of 4-methoxyphenylacetylene (1.0 mmol) in THF (0.5 mL) were added. The vial was closed and the content stirred at rt for 18 h. THF was removed under reduced pressure, Et₂O (20 mL) was added and the organic phase was washed with aqueous NaHCO₃ (5%, 2×10 mL), water (10 mL), aqueous LiCl (1 mol·l⁻¹, 10 mL) and brine (10 mL), dried (MgSO₄), filtered and solvent was removed under reduced pressure. Purification by column chromatography (silicagel) gave the product as a white solid. Yield 77%; m.p. 159-160° C.; IR (CHCl₃, film) ν=1218, 746, 670 cm⁻¹; ¹H NMR (500 MHz, CDCl₃) δ=8.02 (s, 1H), 7.82-7.80 (m, 2H), 7.01-6.99 (m, 2H), 3.87 (s, 3H); ¹³C NMR (125.7 MHz, CDCl₃) δ=160.6, 148.7, 127.7, 121.2, 117.2, 117.1, 114.5, 112.5, 110.9, 110.82, 110.79, 110.3, 109.8, 108.5, 55.5; ¹⁹F NMR (470.4 MHz, CDCl₃) δ=−81.2 (t, ³J_(F—F)=9.9 Hz, CF₃), −95.6 (t, ³J_(F—F)=11.6 Hz, CF₂), −122.0 to −122.5 (m, 3×CF₂), −123.0 to −123.3 (m, 2×CF₂), −126.6 (br s, CF₂); HRMS (EI) m/z calculated for C₁₇H₉₀N₃F₇ [M+H]⁺: 594.04687, found 594.04695.

Example 28: 1-(Trifluoromethyl)-4-(4-(trifluoromethyl)phenyl)-1H-1,2,3-triazole (Two-Step One Pot Synthesis)

CsF (182 mg, 1.2 mmol) was dried in a screw-cap vial overnight under high vacuum at 120° C. Then the vial was cooled to rt, filled with argon, dry DMF (4 mL) was added and the mixture was cooled to −60° C. A solution of CF₃TMS (177 μl, 1.2 mmol) and TosN₃ (153 μl, 1.0 mmol) in dry DMF (1 mL) was added dropwise and the mixture was stirred at −60° C. to −30° C. for 4 h. A solution of (4-trifluoromethyl)phenylacetylene (1.2 mmol) in dry DMF (0.5 mL) and an aqueous solution of CuSO₄.5H₂O (1 mol·l⁻¹, 0.12 mmol, 120 μl) and sodium L-ascorbate (1 mol·l⁻¹, 0.12 mmol, 120 μl) were added. The vial was closed and stirred at rt for 18 h. Water (5 mL) was added, the product was extracted into Et₂O (3×5 mL), the combined organic phase was washed with water (5 mL), aqueous LiCl (1 mol·l⁻¹, 2×5 mL), water (5 mL), dried (MgSO₄), filtered and solvent was removed under reduced pressure. Purification by column chromatography (silicagel) gave the product as a white solid. Yield 50%, m.p. 112-115° C., R_(f) (cyklohexane:EtOAc 97:3)=0.18; IR (CHCl₃, film) ν=1444, 1223, 1204, 1109, 827 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ=8.23 (s, 1H), 8.00 (d, J=8.0 Hz, 2H), 7.73 (d, J=8.1 Hz, 2H); ¹³C NMR (101 MHz, CDCl₃) δ=147.2, 132.1, 131.4 (q, ²J_(C—F)=32.8 Hz, C—CF₃), 126.5, 126.3 (q, ³J_(C—F)=3.7 Hz, C═C—CF₃), 124.0 (q, ¹J_(C—F)=272.1 Hz, C—CF₃), 118.2, 117.7 (q, ¹J_(C—F)=268.7 Hz, N—CF₃); ¹⁹F NMR (376 MHz, CDCl₃) δ=−59.3 (s, 3F, N—CF₃), −63.3 (s, 3F, ArCF₃); HRMS (EI) m/z calculated for C₁₀H₅N₃F₆ [M]⁺: 281.0388, found 281.0391.

Example 29: 4-(4-Fluorophenyl)-1-(trifluoromethyl)-1H-1,2,3-triazole (Two-Step One Pot Synthesis)

CsF (182 mg, 1.2 mmol) was dried in a screw-cap vial overnight under high vacuum at 120° C. Then the vial was cooled to rt, filled with argon, dry DMF (4 mL) was added and the mixture was cooled to −60° C. A solution of CF₃TMS (177 μl, 1.2 mmol) and TosN₃ (153 μl, 1.0 mmol) in dry DMF (1 mL) was added dropwise and the mixture was stirred at −60° C. to −30° C. for 4 h. A solution of 4-fluorophenylacetylene (1.2 mmol) in dry DMF (0.5 mL) and an aqueous solution of CuSO₄.5H₂O (1 mol·l⁻¹, 0.12 mmol, 120 μl) and sodium L-ascorbate (1 mol·l⁻¹, 0.12 mmol, 120 μl) were added. The vial was closed and stirred at rt for 18 h. Water (5 mL) was added, the product was extracted into Et₂O (3×5 mL), the combined organic phase was washed with water (5 mL), aqueous LiCl (1 mol·l⁻¹, 2×5 mL), water (5 mL), dried (MgSO₄), filtered and solvent was removed under reduced pressure. Purification by column chromatography (silicagel) gave the product as a white solid. Yield 81%, m.p. 110-111° C., R_(f) (cyklohexane:EtOAc 97:3)=0.13; IR (CHCl₃, film) ν=1444, 1207, 1011, 823 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ=8.14 (s, 1H), 7.88-7.83 (m, 2H), 7.19-7.13 (m, 2H); ¹³C NMR (101 MHz, CDCl₃) δ=163.4 (d, ¹J_(C—F)=249.3 Hz), 147.7, 128.2 (d, ³J_(C—F)=8.3 Hz), 124.9 (d, ⁴J_(C—F)=3.4 Hz), 117.7 (q, ¹J_(C—F)=268.4 Hz), 117.0, 116.3 (d, ²J_(C—F)=15.1 Hz); ¹⁹F NMR (376 MHz, CDCl₃) δ=−59.3 (s, 3F), −111.9 (ddd, J_(C—F)=13.6, 8.5, 5.5 Hz, 1F); HRMS (EI) m/z calculated for C₉H₅N₃F₄ [M]⁺: 231.0420, found 231.0410.

Example 30: 5-Iodo-1-(pentafluoroethyl)-4-phenyl-1H-1,2,3-triazole

A cooled (−20° C.) mixture of 1-azidopentafluoroethane in THF (2.7 mL, 0.64 mmol), and Et₃N (145 mg, 1.43 mmol) was added dropwise to a cooled mixture of copper(I) phenylacetylide (116 mg, 0.704 mmol) and iodine (164 mg, 0.64 mmol). The mixture was stirred in a closed vial at rt for 16 h. The mixture was then poured onto water (10 mL), extracted with Et₂O (3×10 mL), the combined organic phase was dried (MgSO₄), filtered and solvent was removed under reduced pressure. Purification by column chromatography (silicagel) gave the product as a white solid. Yield 60%, m.p. 119-120° C., ¹H NMR (400 MHz, CDCl₃) δ=7.91-7.89 (m, 2H), 7.54-7.46 (m, 3H); ¹³C NMR (101 MHz, CDCl₃) δ=152.6, 129.7, 128.9, 128.6, 128.5, 117.2 (qt, ¹J_(C—F)=288.8 Hz, ²J_(C—F)=38.4 Hz, CF₃), 112.2 (tq, ¹J_(C—F)=271.7 Hz, ²J_(C—F)=43.4 Hz, CF₂), 71.4; ¹⁹F NMR (376 MHz, CDCl₃) δ=−81.4 (s, 3F), −93.4 (s, 2F); HRMS (EI) m/z calculated for C₁₀H₆N₃F₅I [M+H]⁺: 389.95211, found 389.95225.

Example 31: 4-Phenyl-1-(1,1,2,2-tetrafluoro-2-(phenylthio)ethyl)-1H-1,2,3-triazole

A mixture of (2-azido-1,1,2,2-tetrafluoroethyl)(phenyl)sulfane (83 mg, 0.33 mmol), phenylacetylene (33.7 mg, 0.33 mmol), CuSO₄.5H₂O (3 mg, 0.019 mmol), sodium L-ascorbate (6.5 mg, 0.03 mmol), tris((1-benzyl-1H-1,2,3-triazol-4-yl)methyl)amine (8.8 mg, 0.017 mmol), DMF (3 mL) and water (0.05 mL) was stirred in a closed vial in a microwave at 60° C. for 1 h. The mixture was then poured onto water (10 mL), extracted with Et₂O (3×10 mL), the combined organic phase was dried (MgSO₄), filtered and solvent was removed under reduced pressure. Purification by column chromatography (silicagel) gave the product as a white amorphous solid. Yield 81%, IR (CHCl₃, film) ν=3080, 3060, 1587, 1577, 1494, 1475, 1443, 1308, 1249, 1107, 1081, 1080, 1024, 965, 901, 838, 761, 691, 520 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ=8.04 (t, J=0.7 Hz, 1H), 7.88-7.82 (m, 2H), 7.66-7.60 (m, 2H), 7.49-7.42 (m, 3H), 7.42-7.35 (m, 3H); ¹³C NMR (101 MHz, CDCl₃) δ=148.33, 137.17, 131.07, 129.43, 129.10, 129.01, 128.89, 126.09, 122.67 (t, ⁴J_(C—F)=2.8 Hz), 122.02 (tt, ¹J_(C—F)=291.6, ²J_(C—F)=39.2 Hz, CF₂), 118.25, 113.50 (tt, ¹J_(C—F)=272.3, ²J_(C—F)=35.8 Hz, CF₂); ¹⁹F NMR (376 MHz, CDCl₃) δ=−89.61 (t, ³J_(F—F)=6.3 Hz), −95.56 (t, ³J_(F—F)=6.3 Hz); HRMS (EI) m/z calculated for C₁₆H₁₁F₄N₃S [M]⁺: 353.0610, found 353.0613.

INDUSTRIAL APPLICABILITY

Compounds according to the invention can be used in the production of agrochemicals and biologically active compounds in pharmaceutical industry. 

The invention claimed is:
 1. A method for preparation of azidoperfluoroalkanes and azidopolyfluoroalkanes of formula R_(F)—N₃, wherein R_(F) is selected from the group consisting of C_(n)F_(2n+1), C_(n)F_(x)H_(2n+1−x), C_(n)F_(x)X_(2n+1−x) or R¹CF₂CF₂, wherein n is an integer in the interval from 1 to 10, x is an integer in the interval from 2 to 20 and X is Cl, Br, or I, R¹ is selected from the group consisting of C₁₋₁₀ alkyl, ArO, ArS, imidazolyl, benzimidazolyl, or pyrazolyl and Ar is phenyl or substituted phenyl, said process having the following steps (A) generation of a synthetic equivalent of polyfluoroalkyl carbanion, said synthetic equivalent having the formula [R_(F)]⁻, by a method selected from: a) activation of trialkyl(polyfluoroalkyl)silane of general formula R³ ₃SiR_(F), wherein R³ is C₁₋₅ alkyl, with a Lewis base which is selected from the group consisting of potassium fluoride, cesium fluoride, tetramethylammonium fluoride, tetrabutylammonium fluoride, sodium carbonate, potassium carbonate, potassium phosphate, sodium acetate, potassium acetate, tetrabutylammonium acetate; b) reaction of polyfluoroalkane of general formula R_(F)H with a base which is selected from a group consisting of methyllithium, butyllithium, phenyllithium, Grignard reagent of general formula R³MgX, wherein R³ is C₁₋₅ alkyl, and complexes of these compounds with LiCl; or c) reaction of halopolyfluoroalkane of general formula R_(F)Br or R_(F)I with metalation reagents, which are selected from a group consisting of methyllithium, butyllithium, Grignard reagent of general formula R³MgX, wherein R³ is C₁₋₅ alkyl, and complexes of these compounds with LiCl, at a temperature in the range from −78° C., or from the melting point of the reaction mixture, to +60° C., and (B) reaction of an electrophilic azidation reagent of general formula R²—N₃, wherein R² is selected from the group consisting of n-C₄F₉SO₂, ArSO₂, Br, and I, wherein Ar is phenyl or substituted phenyl, with the synthetic equivalent of polyfluoroalkyl carbanion of general formula [R_(F)]⁻ generated in step (A).
 2. A method for preparation of N-perfluoroalkyl- or N-polyfluoroalkyl-substituted triazoles of formula 1

wherein R_(F) is selected from the group consisting of C_(n)F_(2n+1), C_(n)F_(x)H_(2n+1−x), C_(n)F_(x)X_(2n+1−x) or R¹CF₂CF₂, wherein n is an integer in the interval from 1 to 10, x is an integer in the interval from 2 to 20 and X is Cl, Br, or I, R¹ is selected from the group consisting of C₁₋₁₀ alkyl, ArO, ArS, imidazolyl, benzimidazolyl, or pyrazolyl and Ar is phenyl or substituted phenyl, R⁴ is selected from a group consisting of C₁₋₁₀ alkyl, XCH₂CH₂, COOR³, C(CH₃)₂OH, benzyloxy-C₁₋₄-alkyl, pyridyl, phenyl, and pyridyl or phenyl substituted by a group selected from C₁₋₁₀ alkyl, F, Cl, Br, I, OR³, NO₂, NH₂, CF₃, wherein R³ is C₁₋₅ alkyl, by performing the steps of: (A) generation of a synthetic equivalent of polyfluoroalkyl carbanion, said synthetic equivalent having the formula [R_(F)]⁻, by a method selected from: a) activation of trialkyl(polyfluoroalkyl)silane of general formula R³ ₃SiR_(F), wherein R³ is C₁₋₅ alkyl, with a Lewis base which is selected from the group consisting of potassium fluoride, cesium fluoride, tetramethylammonium fluoride, tetrabutylammonium fluoride, sodium carbonate, potassium carbonate, potassium phosphate, sodium acetate, potassium acetate, tetrabutylammonium acetate; b) reaction of polyfluoroalkane of general formula R_(F)H with a base which is selected from a group consisting of methyllithium, butyllithium, phenyllithium, Grignard reagent of general formula R³MgX, wherein R³ is C₁₋₅ alkyl, and complexes of these compounds with LiCl; or c) reaction of halopolyfluoroalkane of general formula R_(F)Br or R_(F)I with metalation reagents, which are selected from a group consisting of methyllithium, butyllithium, Grignard reagent of general formula R³MgX, wherein R³ is C₁₋₅ alkyl, and complexes of these compounds with LiCl, at a temperature in the range from −78° C., or from the melting point of the reaction mixture, to +60° C., and (B) reaction of an electrophilic azidation reagent of general formula R²—N₃, wherein R² is selected from the group consisting of n-C₄F₉SO₂, ArSO₂, Br, and I, wherein Ar is phenyl or substituted phenyl, with the synthetic equivalent of polyfluoroalkyl carbanion of general formula [R_(F)]⁻ generated in step (A); to obtain the azide R_(F)—N₃, and then performing a cycloaddition reaction of the azide R_(F)—N₃ with alkyne of formula 2

in the presence of copper(I) catalyst at a temperature in the range from −30° C. to the boiling point of the reaction mixture.
 3. A method for preparation of compounds of general formula 3

wherein R_(F) is selected from the group consisting of C_(n)F_(2n+1), C_(n)F_(x)H_(2n+1−x), C_(n)F_(x)X_(2n+1−x) or R¹CF₂CF₂, wherein n is an integer in the interval from 1 to 10, x is an integer in the interval from 2 to 20 and X is Cl, Br, or I, R¹ is selected from the group consisting of C₁₋₁₀ alkyl, ArO, ArS, imidazolyl, benzimidazolyl, or pyrazolyl and Ar is phenyl or substituted phenyl, R⁴ is selected from a group consisting of C₁₋₁₀ alkyl, XCH₂CH₂, COOR³, C(CH₃)₂OH, benzyloxy-C₁₋₄-alkyl, pyridyl, phenyl, and pyridyl or phenyl substituted by a group selected from C₁₋₁₀ alkyl, F, Cl, Br, I, OR³, NO₂, NH₂, CF₃, wherein R³ is C₁₋₅ alkyl, by performing the steps of: (A) generation of a synthetic equivalent of polyfluoroalkyl carbanion, said synthetic equivalent having the formula [R_(F)]⁻, by a method selected from: a) activation of trialkyl(polyfluoroalkyl)silane of general formula R³ ₃SiR_(F), wherein R³ is C₁₋₅ alkyl, with a Lewis base which is selected from the group consisting of potassium fluoride, cesium fluoride, tetramethylammonium fluoride, tetrabutylammonium fluoride, sodium carbonate, potassium carbonate, potassium phosphate, sodium acetate, potassium acetate, tetrabutylammonium acetate; b) reaction of polyfluoroalkane of general formula R_(F)H with a base which is selected from a group consisting of methyllithium, butyllithium, phenyllithium, Grignard reagent of general formula R³MgX, wherein R³ is C₁₋₅ alkyl, and complexes of these compounds with LiCl; or c) reaction of halopolyfluoroalkane of general formula R_(F)Br or R_(F)I with metalation reagents, which are selected from a group consisting of methyllithium, butyllithium, Grignard reagent of general formula R³MgX, wherein R³ is C₁₋₅ alkyl, and complexes of these compounds with LiCl, at a temperature in the range from −78° C., or from the melting point of the reaction mixture, to +60° C., and (B) reaction of an electrophilic azidation reagent of general formula R²—N₃, wherein R² is selected from the group consisting of n-C₄F₉SO₂, ArSO₂, Br, and I, wherein Ar is phenyl or substituted phenyl, with the synthetic equivalent of polyfluoroalkyl carbanion of general formula [R_(F)]⁻ generated in step (A); to obtain the azide R_(F)—N₃, and then performing a cycloaddition reaction of R_(F)—N₃ with alkyne of general formula 4

and with iodine in the presence of tertiary amine as a base, at a temperature in the range from −30° C. to the boiling point of the reaction mixture.
 4. The method according to claim 3, wherein the tertiary amine is selected from trimethylamine, N,N-diisopropylethylamine, N,N,N′,N′-tetramethylethylenediamine, tris((1-benzyl-1H-1,2,3-triazolyl)methyl)amine or tris((1-tert-butyl-1H-1,2,3-triazolyl)methyl)amine. 